Metallic soap composition



Patented Jan. 12, 1943 METALLIC SOAP COMPOSITION Joseph Nothum, Elizabeth, N. J., and Francis J. Licata, New York, N. Y., asslgnors to National Oil Products Company, Harrison, N. J., a corporation of New Jersey No Drawing. Application December 28, 1939, Serial No. 311,286

15 Claims.

This invention relates to metallic soap compositions, more particularly to aluminum ricinoleate compositions and processes for the preparation thereof.

As is well known in the art, aluminum soaps such as aluminum stearate, aluminum palmitate and the like, may be dissolved in solvents such as toluol, etc. in order to form solutions which are useful for water-proofing materials such as bricks, cloth, paper, etc. While these solutions have many valuable properties and have been widely used, the aluminum soaps are ordinarily not very soluble in easily available solvents, as is evidenced by the fact that the solutions now on the market usually contain only about 2 to 3% of the metallic soap; hence storage or transportation of such solutions necessitates storing or transporting large quantities of solvent, which, is not particularly economical. Moreover, it is usually not feasible to store or ship the aluminum soap and then prepare the desired solution when needed, since these soaps tend to become more and more insoluble with age. Therefore, there has been an extensive demand in the industry for stable aluminum soap solutions containing substantially more than 2 to 3% of the soap..

It has been proposed to employ aluminum soap solutions for water-proofing textiles. This proposal has met with some degree'of success because of the excellent water-proofing properties imparted to the textiles by the aluminum soaps. However, it has been found that most aluminum soaps, e. g. aluminum stearate, are relatively soluble in hydrocarbon solvents such as naphthas and the like, and hence tend to be washed from textiles when the textiles are subjected to dry cleaning operations. As yet no satisfactory aluminum soap has been developed which is capable of water-proofing textiles and at the same time resisting the solvent action of dry cleaning solvents.

It is an object of this invention to provide concentrated solutions of aluminum soaps which may be employed for water-proofing purposes.

It is a further object of this invention to provide solutions of aluminum soaps which may be employed for producing water-proof textile materials capable of retaining their water-proof characteristics even when subjected to the action of dry cleaning solvents.

We have made the surprising discovery that freshly prepared aluminum ricinoleate may be dissolved in lacquer solvents so as to form solutions containing as high as about or more of the aluminum soap. The term .lacquer sol vent is used herein to denote those solvents commonly used in the manufacture of lacquers and is thus intended to include low molecular weight esters such as ethyl acetate and amyl acetate, low molecular weight ketones such as acetone, aliphatic alcohols containing up to 6 carbon atoms, solvents such as furfural and mixtures of such solvents with thinners such as toluol. As is well known, aluminum soaps are ordinarily manufactured by preparing an alkali soap of the fatty acid, reacting aluminum sulfate with the alkali soap to precipitate the aluminum soap and then washing the precipitated mass. We prefer to prepare the concentrated solutions of our invention by immediately taking up washed aluminum ricinoleate in wet condition prepared in this manner in a lacquer solvent, whereby a solution of the aluminum ricinoleate in the solvent is formed, the water separating from this solution. However, we may also prepare these concentrated solutions by precipitating the aluminum ricinoleate in the presence of a lacquer solvent, whereby the desired aluminum ricinoleate solution forms and separates from the aqueous material. The preferred solutions of our invention contain from about 30% to about 50% aluminum ricinoleate; however, our process may be employed to prepare any solution containing up to about 50% or more aluminum ricinoleate. The preferred solutions of our invention may be stored or shipped more economically than solutions of aluminum soaps heretofore prepared because of the exceedingly high concentration of aluminum soap contained therein.

We have also found that the aluminum ricinoleate solutions of our invention may be employed to great advantage for water-proofing textiles. As is well known, textiles are ordinarily waterproofed with an aluminum soap by impregnating the textiles with a solution of the aluminum soap and then permitting the solvent to evaporate. We have found that coatings of aluminum ricinoleate applied to textiles in such a manner are highly flexible and produce excellent waterproofing effects. What is even more surprising, however, is the fact that textiles water-proofed with aluminum ricinoleate in accordance with our invention strongly resist the solvent action of dry cleaning solvents, such as naphthas, so that they may be subjected to any number of dry cleaning operations without substantially losing their water-proof properties.

As pointed out above, we prefer to prepare the aluminum ricinoleate solutions of our invention by agitating a lacquer solvent with wet, freshly prepared aluminum ricinoleate. The. aluminum ricinoleate may be prepared by the addition of a solution of aluminum sulfate to a solution of sodium ricinoleate containing, for example, about 25% of the sodium soap. This precipitation may be advantageously carried out at a temperature around 90 0., although other temperatures may be employed, as is well known in the an. After precipitation of the aluminum soap the mother liquor may be decanted and the mass washed, whereby a wet aluminum ricinoleate mass remains. The solutions of our invention may then be prepared by adding a suitable amount of a lacquer solvent to the wet aluminum ricinoleate and thoroughly agitating the mixture. Among the solvents which we have found to be highly suitable for the preparation of such solutions may be mentioned ethanol, butanol, amyl acetate, ethyl acetate, a mixture of equal parts of amyl acetate and butanol, and mixtures of the above solvents with thinners such as toluol. The amount of solvent employed in order to prepare these solutions will depend upon the amount of aluminum ricinoleate to be dissolved and upon the desired concentration of the aluminum ricinoleate solution to be prepared. Since we prefer to prepare solutions containing from 30% to 50% aluminum ricinoleate, the amount of solvent preferably added to the wet mass should be sufficient to yield such solutions. The wet aluminum ricinoleate may be agitated with the lacquer solvent at any desired temperature; thus, for example, it may be found advantageous in certain cases to employ elevated temperatures in order to accelerate the formation of the desired solution. After the wet mass has been thoroughly agitated with the solvent, the mixture may be permitted to stand whereby two layers form. One layer contains the solution of the aluminum ricinoleate and the other layer is the aqueous layer which separates from the aluminum ricinoleate solution. These layers are separated and the aluminum ricinoleate solution recovered. In some cases it may be found that this solution is somewhat hazy due to the presence of small amounts of water; this haziness may be removed by drying the solution with anhydrous sodium sulfate or other suitable drying agent.

The concentrated aluminum ricinoleate solutions may also be prepared by precipitating aluminum ricinoleate in the presence of a lacquer solvent; thus, for example, an aqueous solution containing about 25% sodium ricinoleate may be prepared and a suitable amount of a lacquer solvent then added thereto. An aluminum sulfate solution may then be added to the mixture with agitation, whereby a solution of aluminum ricinoleate in the lacquer solvent is formed which separates from the aqueous material. In order to effect a complete separation of the aluminum ricinoleate solution, it may be desirable to heat the solution so as to break any emulsions.

It is to be understood that the methods described above for the preparation of the aluminum ricinoleate solutions of our invention are preferred methods and that these solutions may also be prepared by other processes known to the art. It should be borne in mind, however, that it is highly desirable to prepare such solutions from freshly prepared aluminum ricinoleate, since the solubility of this soap in lacquer solvents decreases after it has been permitted to stand for extended periods of time.

The solutions of our invention are perfectly stable and may be stored and shipped as desired.

These solutions may be diluted with lacquer solvents in order to form solutions having concentrations suitable for water-proofing purposes; ordinarily solutions containing from about 3% to about 10% aluminum ricinoleateare most suitable for use in this connection. Other aluminum soaps may be added to these solutions in order to modify their properties; thus, for example, aluminum stearate or the aluminum soap of hydrogenated castor oil may be included in the solutions. When incorporating other aluminum soaps in the solutions of our invention, it is sometimes advantageous to add small quantities of solvents, such as toluol, capable of readily dissolving these soaps. uther ingredients such as emulsifiers, stiffeners, plasticizers, etc., compatible with the lacquer solvents may also be incorporated in these solutions in order to modify or improve their properties.

The solutions of our invention may be employed for water-proofing fibrous material of all kinds, particularly textiles. We have conducted several tests to .determine the resistance of aluminum ricinoleate to the solvent action of dry cleaning solvents; these tests have invariably indicated that textiles water-proofed by impregnation with a solution of aluminum ricinoleate prepared in accordance with our invention may be subjected to any number of dry cleaning operations without substantial loss in their waterproof characteristics. It will be recognized that this hitherto unknown property of aluminum ricinoleate is highly valuable, since, to our knowledge, no other aluminum soap now on the market successfully resists prolonged solvent action of dry cleaning solvents. The aluminum ricinoleate solutions of our invention may also be employed for water-proofing bricks and similar articles, for improving the transparency of paper and for other uses well known to the art.

The following examples are illustrative of our invention. Amounts are given in parts by weight.

Example I Aluminum ricinoleate was prepared by adding a sufllcient amount of an aluminum sulfate solution to a 25% sodium ricinoleate solution, the mixing being carried out at a temperature of C. The aqueous solution was then decanted from the aluminum ricinoleate precipitate; the wet residue contained about equal quantities of water and solid material. About 200 parts of the wet mass were then agitated with about parts of butanol, whereby a thin emulsion was formed. After standing overnight, this emulsion separated into an aqueous layer and a layer containing aluminum ricinoleate dissolved in butanol. The butanol layer was separated from the aqueous layer and dried with anhydrous sodium sulfate, forming a clear solution. This solution was then analyzed and it was found to contain about 47% aluminum ricinoleate.

Example II A solution of aluminum ricinoleate in amyl acetate was prepared as described in Example I, employing 100 parts of amyl acetate in place of the butanol used in that example. This solution contained about 31% aluminum ricinoleate.

Example III A solution of aluminum ricinoleate in a mixture of butanol and amyl acetate was prepared as described in Example I, employing a mixture of 50 parts of butanol and 50 parts of amyl acetate in place of the butanol used in that example. This solution contained about 51% aluminum ricinoleate.

Example IV A solution of 80 parts of sodium ricinoleate in about 80 parts of water were mixed with 100 parts of amyl acetate. '75 parts of aluminum sulfate were dissolved in water and the solution was gradually added to the mixture with agitation. The mixture was then heated to about 70 0., whereby two layers formed. The lower layer, consisting of an aqueous solution containing sodium sulfate, was discarded. The upper layer containing aluminum ricinoleate dissolved in the amyl acetate was withdrawn and dried with anhydrous sodium sulfate. An analysis of this solution indicated that it contained about 43% aluminum ricinoleate.

Example V A solution of aluminum ricinoleate in butanol was prepared as described in Example IV, employing 100 parts of butanol in place of amyl acetate used in that example. This solution also contained about 43% aluminum ricinoleate.

Example VI A sample of woolen cloth was water-proofed by immersing the cloth in a solution of aluminum ricinoleate in butanol prepared by diluting the solution made in accordance with Example I, and then evaporating the solvent from the impregnated cloth. It was found that the waterprooied cloth could be contacted with dry cleaning solvents for prolonged periods of time without losing its water-proof characteristics.

It will be evident from the above description that our invention provides new and valuable aluminum soap compositions which may be employed to great advantage for water-proofing articles of all types. Because of the large amounts of aluminum ricinoleate which may be incorporated in the lacquer solvents in accordance with our invention, our compositions may be shipped or stored on a far more economical basis than heretofore possible. Furthermore, the unique resistance of aluminum ricinoleate to the solvent action of dry cleaning solvents makes this metallic soap superior to any metallic soap heretofore employed for water-proofing cloth. Therefore, our invention will undoubtedly be of great interest to those engaged in the manufacture of aluminum and other metallic soaps.

Since certain changes in carrying out the above process and certain modifications in the compositions which embody the invention may be made without departing from its scope, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

Having described our invention, what we claim as new and desire to secure by Letters Patents is:

1. A composition of matter comprising chiefly a solution of aluminum ricinoleate in a lacquer solvent, the concentration of the aluminum ricinoleate being between about 30% and about 50%.

2. A composition of matter comprising chiefly a solution of aluminum ricinoleate in butanol, the concentration of the aluminum ricinoleate being between about 30% and about 50%.

3. A composition of matter comprising chiefly a solution of aluminum ricinoleate in amyl acetate, the concentration of the aluminum ricinoleate being between about 30% and about 50%.

4. A composition of matter comprising chiefly a solution of aluminum ricinoleate in a mixture of butanol and amyl acetate, the concentration of the aluminum ricinoleate beingbetween about 30% and about 50%. g

5. A process for preparing solutions of aluminum ricinoleate which comprises agitating wet. freshly prepared aluminum ricinoleate with a lacquer solvent, and separating the solution of aluminum ricinoleate in said solvent from the aqueous material, the amount of solvent employed being sufficient to form a solution containing between about 30% and about 50% aluminum ricinoleate.

6. A process for preparing solutions of aluminum ricinoleate which comprises agitating wet, freshly prepared aluminum ricinoleate with butanol, and separating the solution of aluminum ricinoleate in butanol from the aqueous material. the amount of butanol employed being suiiicient to form a solution containing between about 30% and about 50% aluminum ricinoleate.

7. A process for preparing solutions of aluminum ricinoleate which comprises agitating wet, freshly prepared aluminum ricinoleate with a mixture of butanol and amyl acetate, and separating the solution of aluminum ricinoleate in the mixture of butanol and amyl acetate from the aqueous material, the amount of the mixture of butanol and 'amyl acetate employed being sumcient to form a solution containing between about 30% and about 50% aluminum ricinoleate.

8. A process for preparing solutions of aluminum ricinoleate which comprises mixing a lacquer solvent with an aqueous solution of an alkali ricinoleate. adding aluminum sulfate to the 7 mixture, agitating the reaction mass so as to form a solution of the aluminum ricinolate in the solvent, and separating the solution thus formed from the aqueous material, the amount of lacquer solvent employed being sufficient to form a solution containing between about 30% and about 50% aluminum ricinoleate.

9. A process for preparing solutions of aluminum ricinolate which comprises mixing amyl acetate with an aqueous solution of sodium ricinoleate, adding aluminum sulfate to the mixture, agitating the reaction mass so as to form a solution of the aluminum ricinoleate in the amyl acetate, and separating the solution thus formed from the aqueous material, the amount of amyl acetate employed being suflicient to form a solution containing between about 30% and about 50% aluminum ricinoleate.

10. A process for water-proofing fibrous materials which comprises impregnating the fibrous material with a solution of aluminum ricinoleate in a lacquer solvent and evaporating the solvent from the impregnated material.

11. Textile material having a uniform, flexible coating of aluminum ricinoleate, said material being substantially water-proof and said coating being resistant to the action of dry cleaning solvents.

12. Fibrous material impregnated with aluminum ricinoleate, said material being resistant to water and dry cleaning solvents.

13. A process for preparing solutions of aluminum ricinoleate which comprises adding a weter-soluble aluminum salt to an aqueous solution of a water-soluble soap of ricinoleic acid to precipitate out aluminum ricinoleate and agitating the wet, freshly prepared aluminum ricinoleate with a lacquer solvent.

14. A process for preparing solutions of aluminum ricinoleate which comprises adding. a we.-

tar-soluble aluminum salt to an aqueous solution 15. A waterproofing composition comprising a of a water-soluble soap or ricinoleic acid to presolution of aluminum ricinoleate in a lacquer solcipitate out aluminum ricinoleate, said precipitavent. the concentration or the aluminum ricintion step being carried out in the presence or a. oleate being between about 3% and about 10%. lacquer solvent and agitating the mass to cause 5 the freshly prepared aluminum ricinoleate to dis- JOSEPH NOTHUM. solve in the lacquer solvent. FRANCIS J. LICATA.

CERTI F ICATE OF C ORRECTI 0N Patent No. 2,507,852. January 12, 1914.5.

JOSEEH NOTHUI'I, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows{ Page 5, sec- 0nd column, line 514., beginning with "10. A'process for" strike out all to and including the word and period "material." in line 58, comprising claim 10, andfor the claims now numbered "11", "12", "15" "114." and "15" read --lO'--, --ll-, -12--, --15-- and -Z ll4.--, respectively, and in the. heading to the printed specification, line 8, for "15 Claims. read "114. C -"3 and thfit the said Letters Patent should be read with this 'cor rection therein that the same may confcm to the record of the case in the Patent Office.

Signed and sealed this 16th day of February, A. D. 19!),5.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents. 

